Optically active compounds and a method for producing them

ABSTRACT

The present invention provides special epoxy derivative (1), cyclohexanone derivative (2), cyclohexenone derivative (3) and 3-substituted cyclohexenone derivative (4) which are useful as intermediates for synthesizing physiologically active materials, and a method for stereoselectively introducing substituted groups. Further, the present invention provides a method for synthesizing optically active compounds, such as optically active carvone via these intermediates. ##STR1##

This is a division of parent application Ser. No. 08/277,006, filed Jul.19, 1994 now U.S. Pat. No. 5,446,175.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to epoxy derivatives useful as startingmaterials for synthesizing various physiologically active materials anda method of producing the derivatives, cyclohexanone derivatives,cyclohexenone derivatives, 3-substituted cyclohexanone derivatives, anda method of producing optically active carvone of perfume via thesederivatives.

2. Description of the Prior Art

Epoxy derivatives, cyclohexanone derivatives, and 3-substitutedcyclohexanone derivatives of the present inventions are widely useful asstarting materials for synthesizing various physiologically activematerials such as medicines and agricultural medicines, particularlythese derivatives are very useful as starting materials for synthesizingoptically active carbons of perfumes and their intermediates. Hitherto,a method for efficiently introducing substitution groupsstereoselectively into cyclohexa-2, 5-diene skeletons (6) is unknown.For example, as a conventional method of optically active carvones, areaction method of hydration of d-limonene with synthetic zeolite (NihonKagakukaishi, (1), pages 63-67 (1992)), a methol of stereoselectiveGrignard reaction with optically active 5-trimethylsilyl-2-cyclohexenoneas a starting material (Takei et al, Tetrahedron Lett., 30, 7075 (1989))and the like have been known. The former method is not stereoselectivein the reaction, so that optically active icarvone should be isolatedfrom five kinds of products, the steps are troublesome and the productis obtained in low yield (30%). The latter method is stereoselective, byoptically active 5-trimethylsilyl-2-cyclohexenone, which is a startingmaterial having a stereoselectively 5-substituted group, should beobtained by repeated recrystallization of a diastereomer saltsynthesized from a racemate of the starting material with cinchonidineand toluenethiol, and it is obtained in a low yield of 3% fromracemic-5-trimethylsilyl-2-cyclohexenone. Thus, prior to the presentinvention, there is no industrially excellent method for producingefficiently optically active carvones.

Accordingly, it is desired to find an efficient method for producingoptically active carvones. Further, it is desired to find opticallyactive intermediates such as epoxy derivatives of the present inventionobtained by deriving stereoselectively a substituted group,cyclohexanone derivatives, cyclohexenone derivatives, and 3-substitutedcyclohexanone derivatives, which are widely applicable.

SUMMARY OF THE INVENTION

Considering the above, the inventors of the present invention haveearnestly studied to obtain a retro synthetic method as shown in thefollowing: ##STR2##

Namely, it has been found that several kinds of substituted groups areeasily and stereoselectively introduced to 2,5-dienone (6) by using acompound (7) or (7') having a tricyclo ring skeleton as a startingmaterial in good optical purities.

Further, by using the compound (7) having a tricyclo ring skeleton as astarting material, new useful epoxy derivative (1) or (1'),cyclohexanone derivative (2) or (2'), cyclohexenone (3) or (3') and3-substituted cyclohexanone derivative (4) or (4') are obtained. Then, amethod for efficient by obtaining the optically active compoundrepresented by the formula (5) or (5') via the above derivatives.

In the present invention, the method is characterized in that, after thetricyclo ring compound (7) is epoxidized, a substituted group isstereoselectively introduced into the compound. The resultant compoundsare epoxy derivatives represented by the formula: ##STR3## wherein R isalkyl, a hydrocarbon residue having at least one unsaturated bond,aralkyl or hydrogen, cyclohexanone derivatives represented by theformula: ##STR4## wherein R is alkyl, a hydrocarbon residue having atleast one unsaturated bond, aralkyl or hydrogen, cyclohexenonederivatives represented by the formula: ##STR5## wherein R is alkyl, ahydrocarbon residue having at least one unsaturated bond, aralkyl orhydrogen, and 3-substituted cyclohexanone derivatives represented by theformula: ##STR6## wherein R is alkyl, a hydrocarbon residue having atleast one unsaturated bond or aralkyl, R' is alkyl, a hydrocarbonresidue having at least one unsaturated bond, aralkyl or a substitutedgroup comprising hydrocarbon having trialkyl silyl in the skeleton, areprovided. Moreover, a method for producing the epoxy derivativesrepresented by the formula (1) or (1') characterized in that thetricyclo ring skeleton compound (7) or (7') is epoxidized and asubstituted group is stereoselectively introduced into the compound, anda method for producing the optically active compounds represented by theformula: ##STR7## via these derivatives is provided.

The optically active compound (7) or (7') having a tricyclo ringskeleton, which is a starting material, can be synthesized by thefollowing method: ##STR8##

Namely, the compound (9) is obtained by reduction of a carbonyl group ofthe compound (8), which is obtained by Dieis-Alder reaction withcyclopentadiene and hydroquinone, in the presence of a reducing agentsuch as lithium aluminum hydride. The resultant compound (9) isintroduced to the compound (7) or (7') by a method of Takano et al(Japanese Patent Application Number 4-290684). In particular, thecompound (9) is reacted by transesterification in a solvent such asacetonitrile with fatty acid vinyl esters in the presence of lipase PS(manufactured by Amano Pharmaceutical Co., Ltd. ) derived from aPseudomonas genus, and the optically active compound (10) can beobtained.

Compound (10) may be refluxed with ammonium bicarbonate in a solvent ofdioxane or acetonitrile in the presence of bistriphenylphosphinepalladium chloride to obtain the compound (7).

The compound (7'), which is an enantiomer of the compound (7), may beobtained by esterification of the compound (10) with pivaloylic acidanhydride, selective hydrolysis of the acetate of the resultant compound(11) with potassium carbonate, and reflux of the hydrolyzed compound ina solvent of dioxane or acetonitrile with ammonium bicarbonate in thepresence of bistriphenylphosphine palladium chloride.

The method of producing optically active carvones using the resultantcompound (7) as a starting material is shown in the following: ##STR9##

Firstly, the compound (7) is oxidized with an oxidizing agent such ashydroperoxide to obtain an epoxy derivative (1-1, R=H). Then, ahalogenated material is derived from the epoxy derivative with a basefor drawing protons such as potassium-t-butoxide and the epoxyderivative (1) having a substituted group is obtained. As halogens ofthe halogenated material, chlorine, bromine, iodine and the like areexemplified. As the substituted group, alkyl, a hydrocarbon residuehaving at least one unsaturated bond or aralkyl can be exemplified, andparticularly methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl,t-butyl, pentyl, hexyl, heptyl, octyl, vinyl, allyl, 1-butenyl,2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 1,3-pentadienyl,cyclopropyl, cyclopentyl, 2-cyclopenten-1-yl, 3-cyclopenten-1-yl,2-cyclohexen-1-yl, 3-cyclohexen-1-yl, phenyl, benzyl, o-tolyl, m-tolyl,p-tolyl, 2,3-xylyl, 2,4-xylyl, 3,5-xylyl, o-methoxyphenyl,m-methoxyphenyl, p-methoxyphenyl, o-benzyoxyphenyl, m-benzyloxyphenyl,p-benzyloxyphenyl, 2,3-dimethoxyphenyl, 1,2,4-dimethoxyphenyl,3,5-dimethoxyphenyl, 2,3-dibenzyloxyphenyl, 2,4-dibenzyloxyphenyl and3,5-dibenzyloxyphenyl.

Further, the epoxy derivative (1) may be reacted with a reducing agentsuch as sodium borohydride in the presence of diphenyl diselenide, andthe oxysilane ring is stereoselectively reduced to obtain thecyclohexane derivative (2).

After the cyclohexane derivative (2) is mesylated with a halogenatedsulfonyl compound such as mesyl chloride (MsCl), the resultant mesylatecan be changed to the cyclohexenone derivative (3) by using a base suchas 1,8-diazabicyclo 5.4.0!undeca-7-ene (DBU). The cyclohexenonederivative (3) may be changed to the 3-substituted cyclohexanonederivative (4) by a reaction for introducing substituted groups such asa Grignard reaction. Substituted group R' is alkyl, a hydrocarbonresidue having at least one unsaturated bond, aralkyl or hydrocarbonresidue having at least one trialkylsilyl in the skeleton, andparticularly, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl,t-butyl, pentyl, hexyl, heptyl, octyl, vinyl, allyl, 1-propenyl,1-butenyl, 2-butenyl, 3-butenyl, isopropenyl, 1,2-butadienyl,1,3-butadienyl, 2,3-butadienyl, 1-pentenyl, 2-pentenyl, 3-pentenyl,4-pentenyl, 1,2-pentadienyl, 1,3-pentadienyl, 1,4-pentadienyl,2,3-pentadienyl, 2,4-pentadienyl, 3,4-pentadienyl, cyclopropyl,cyclopentyl, 2-cyclopentene-1-yl, 3-cyclopentene-1-yl,2-cyclohexene-1-yl, 3-cyclohexene-1yl, phenyl, benzyl, o-tolyl, m-tolyl,p-tolyl, 2,3-xylyl, 2,4-xylyl, 3,5-xylyl, o-methoxyphenyl,m-methoxyphenyl, p-methoxyphenyl, o-benzyloxyphenyl, m-benzyloxyphenyl,p-benzyloxyphenyl, 2,3-dimethoxyphenyl, 2,4-dimethoxyphenyl,3,5-dimethoxyphenyl, 2,3-dibenzyloxyphenyl, 2,4-dibenzyloxyphenyl,3,5-dibenzyloxyphenyl, trimethylsilylmethyl, 1-trimethylsilylethyl,2-trimethylsilylethyl, 1-trimethylsilylpropyl, 2-trimethylsilylpropyl,2-trimethylsilylpropyl, 3-trimethylsilylpropyl, 1trimethylsilylvinyl,2-trimethylsilylvinyl, trimethylsilylethynyl or the like.

In these compounds, 3-substituted cyclohexanone derivative (4) wherein Ris Me and R' is isopropenyl can be changed to the (-)i-carvone (5) byretro Diels Alder reaction.

Similarly, the antipode compound (7') having a tricyclo ring skeletonmay be selected as a starting material to obtain the (+) -carvone (5').

The present invention can provide the following merits.

1. Derivatives represented by the above formulas (1) or (1'), (2) or(2'), (3) or (3'), and (4) or (4'), which are useful for synthesizingvarious physiologically active materials such as medicines andagricultural medicines, are obtained.

2. Various substituted groups can be stereoselectively introduced to the2,5-dienone (6).

3. Through the derivatives represented by the formulas (1) or (1'), (2)or (2'), (3) or (3'), and (4) or (4') in order, optically activecompounds represented by the formula (5) or (5') can be obtained.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following examples illustrate the present invention morespecifically, but these are not intended as a definition of the limitsof the invention.

REFERENCE EXAMPLE 1

To an acetonitrile solution (5 ml) of a compound (9) (200 mg, 1.10 mol)and vinyl acetate (0.3 ml, 3.36 mmol), lipase PS (100 mg) was suspended,and the mixture was stirred for two weeks at room temperature. After thelipase was filtered away, the filtrate was concentrated under reducedpressure, and the residue was purified with a chromatograph over silicagel to obtain the colorless optically active compound (10) (193 mg,79%).

REFERENCE EXAMPLE 2

To an acetonitrile solution 2 ml of the optically active compound (10)(100 mg, 0.45 mmol), ammonium bicarbonate (41 mg) andbiistriphenylphosphine palladium chloride (3 mg, 0.004 mmol) were added,the mixture was refluxed for 20 minutes, and diethyl ether (10 ml) wasadded. The ether layer was washed with a saturated aqueous solution ofsodium bicarbonate and with a saturated solution of sodium chloride, andthen the organic layer was dried over magnesium sulfate. The solvent wasdistilled away under reduced pressure, and the residue waschromatographed over silica gel to obtain the compound (7) (72.2 mg,90%).

REFERENCE EXAMPLE 3

To a dichloromethane solution (1 ml) of the optically active compound(10) (139 mg, 0.624 mmol), triethylamine (0.35 ml, 2.5 mmol),4-dimethylamino pyridine DMAP (5 mg, 0.04 mmol) and pivalionic acidanhydride (0.38 ml, 1.9 mmol) were added, and the mixture was stirredfor three days at room temperature. After water (5 ml) was added, themixture was extracted with methylene chloride, the organic layer waswashed with a saturated solution of sodium bicarbonate and with asaturated solution of sodium chloride, and the organic layer was driedover anhydrous magnesium sulfate. The solvent was distilled away underreduced pressure, the residue was chromatographed over silica gel toobtain the crude cyclohexene diester. The diester was dissolved inmethanol (3 ml) as it is, potassium carbonate (50 mg, 0.36 mmol) wasadded, and the mixture was stirred for one hour. After methylenechloride was added, the organic layer was washed twice with a saturatedsolution of sodium chloride and dried over magnesium sulfate. Thesolvent was distilled away under reduced pressure, and the residue waschromatographed over silica gel to obtain the colorless solid compound(12) (132 mg, 80%).

REFERENCE EXAMPLE 4

Using the same method with Reference example 2 except that the compound(12) (94 mg, 0.359 mmol), ammonium carbonate (34 mg, 0.54 mmol) ,bistriphenylphosphine palladium chloride (2.5 mg, 0.0035 mmol) andacetonitrile (3 ml) were used, the compound (7') (57.6 mg, 90%) wasobtained.

EXAMPLE 1

To a methanol solution (20 ml) of the compound (7) (1.83 g, 11.4 mol), a0.5M solution (2.5 ml) of sodium hydroxide and a 30% !(w/v)hydroperoxide solution (2.0 ml, 17.4 mmol) were added on ice cooling andthe mixture was stirred for 20 minutes. Methylene chloride (20 ml) wasadded to the reaction mixture, and the mixture was washed with water andwith a saturated solution of sodium chloride. The organic layer wasdried over anhydrous magnesium sulfate, and the solvent was distilledaway under reduced pressure. The residue was chromatographed over silicagel to obtain a colorless solid of the epoxy derivative (1-1) (1.82 g,yield 90%).

m.p.: 51-52.5° C.; α!_(D) ³⁰ -9.6° (c 1.10, CHCl₃); IR (neat): 1710 cm⁻¹; ¹ H-NMR (300 MHz, CDCl₃ ) δ: 1.14 (d, 1H, J=8.4 Hz ), 1.22 (dd, 1H,J=14.7, 10.6 Hz), 1.31 (d, 1H, J=8.4 Hz), 2.28 (ddd, 1H, J=14.7, 6.6,3.7 Hz), 2.61-2.74 (m, 2H), 2.78 (dd, 1H, J=10.2, 3.3 Hz), 2.98 (br. s,1H), 3.03 (d, 1H, J=4.4 Hz), 3.31 (t, 1H, J=4.4 Hz), 5.76-5.79 (m, 1H),6.08-6.10 (m, 1H); ¹³ C-NMR (75 MHz, CDCl₃) δ: 27.40, 36.25, 42.85,45.43, 47.58, 50.50, 54.47, 57.47, 133.97, 138.39, 209.28 MS m/z: 176(M.sup. +), 66 (100%); HRMS Calcd. C₁₁ H₁₂ O₂ :176.0837. Found:176.0850; Anal Calcd. C₁₁ H₁₂ O₂ : C,74.97, H,6.86 Found: C,74.85,H,6.99

EXAMPLE 2

To a solution of potassium t-butoxide (694 mg, 6.18 mmol) in THF (6 ml),a solution of epoxy derivative (1-1) (545 mg, 3.10 mmol) in THF (5 ml)was added dropwise with stirring at -78° C. After the mixture wasstirred for one hour, methyl iodide (0.60 ml, 9.6 mmol) was added andstir for more one hour at the same temperature. To the resultingreaction mixture, a saturated aqueous solution (10 ml) of ammoniumchloride was added, and the temperature was raised to room temperature.After the reaction mixture was extracted with diethyl ether, extractedliquid was washed width a saturated aqueous solution of sodiumbicarbonate and with a saturated aqueous solution of sodium chloride.Then, the organic layer was dried over anhydrous magnesium sulfate, andthe solvent was distilled away under reduced pressure. The residue waschromatographed over silica gel to obtain the colorless solid epoxyderivative (1) (R=Me, 497 mg, yield 84%).

m.p.: 60°-61° C.; α!_(D) ²⁹ +94.3° (C 1.37, CHCl₃); IR (nujol): 1708cm⁻¹ ; ¹ H-NMR (300 MHz, CDCl₃) δ: 1.32-1.42 (m, 2H), 1.42 (s, 3H), 1.55(d, 1H, J=8.8 Hz), 2.29 (td, 1H, J=10.5, 3.3 Hz), 2.48 (ddd, 1H, J=14.7,7.7, 3.3 Hz), 2.77 (br. s, 2H), 3.17 (d, 1H, J=4.0 Hz), 3.43 (t, 1H,J=4.2 Hz), 5.93 (dd, 1H, J=5.5, 2.9 Hz), 6.25 (dd, 1H, J=5.5, 2.9 Hz);MS m/z: 190 (M⁺), 66 (100%); HRMS Calcd. C₁₂ H₁₄ O₂ : 190.0994 Found:190.1004; Anal Calcd. C₁₂ H₁₄ O₂, C,75.76, H,7.42 Found: C,75.55, H,7.47

EXAMPLE 3

To an ethanol solution (25 ml) of diphenyldiselenide (1.45 g, 4.64mmol), sodium boron hydride (343 mg, 9.2 mmol) was slowly added on icecooling. After the mixture was stirred for 50 minutes at roomtemperature, acetic acid (0.09 ml, 1.5 mmol) was added. After stirringfor 30 minutes, an ethanol solution (5 ml) of the epoxy derivative (1)(441 mg, 2.32 mmol) was added dropwise to the mixture. After the mixturewas stirred for 12 hours, water was added, and the mixture was extractedwith ethyl acetate. The extract was washed with a saturated aqueoussolution of sodium bicarbonate, and with a saturated aqueous solution ofsodium chloride. The organic layer was dried over anhydrous magnesiumsulfate, and the solvent was distilled away under reduced pressure. Theresidue was chromatographed over silica gel to obtain the colorless oilycyclohexanone derivative (2) (R=Me, 400 mg, yield 90% ).

α!_(D) ²⁹ -89.6 (c 1.30, CHCl₃); IR (neat): 1690 cm⁻¹ ; ¹ H-NMR (300MHz, CDCl₃) δ: 1.14-1.24 (m, 1H), 1.44(s, 3H), 1.61 (br. s, 3H),2.10-2.19(m, 2H) , 2.41-2.46 (m, 2H), 2.83 (br. s, 1H), 2.88 (br. s,1H), 4.25 (br. s, 1H), 6.03-6.06 (m, 1H), 6.17-6.20 (m, 1H); ¹³ C-NMR(75 MHz, CDCl₃) δ: 27.34, 35.14, 44.36, 46.12, 47.02, 47.48, 52.01,54.83, 66.27, 135.22, 139.06, 217.18; MS m/z: 192 (M⁺), 66 (100%); HRMSCalcd. C₁₂ H₁₆ O₂ : 192.1151 Found: 192.1142

EXAMPLE 4

To a methylene Chloride solution (5 ml) of the cyclohexanone derivative(2) (R=Me, 400 mg, 2.08 mol), 1,8-diazabicyclo 5.4.0!undeca-7-ene (0.31ml, 2.0 mmol), triethyl amine (0.58 ml, 4.2 mmol) and mesyl chloride(0.24 ml, 3.1 mmol) were added on ice cooling, and the mixture wasstirred at room temperature for 3 hours. Further, 1,8-diazahicyclo5.4.0! 7-ene (0.31 ml, 2.0 mmol ) and mesyl chloride (0.08 ml, 1.0 mmol) were added to the mixture and the mixture was stirred at roomtemperature for 2 hours. Water was added to the resulting reactionmixture. After the mixture was extracted with diethyl ether, the organiclayer was washed with a saturated aqueous solution of sodium bicarbonateand with a saturated solution of sodium chloride. Then, the organiclayer was dried over anhydrous magnesium sulfate, and the solvent wasdistilled away under reduced pressure. The residue was chromatographedover silica gel to obtain the colorless solid cyclohexenone derivative(3) (R=Me, 338 mg, yield 93% ).

m.p.: 87°-88° C.; α!_(D) ²⁹ -144° (c 0.994, CHCl₃); IR (neat): 1660 cm⁻¹; ¹ H-NMR (300 MHz, CDCl₃) δ: 1.29 (s, 3H), 1.29-1.31 (m, 1H), 1.49 (d,1H, J=8.8 Hz), 1.95 (dd, 1H, J=20.9, 3.3 Hz), 2.23 (dt, 1H, J=10.2, 3.3Hz), 2.59 (ddt, 1H, J=20.9, 10.2, 3.1 Hz), 2.81 (br. s, 1H), 2.86 (br.s, 1H), 5.72 (br. d, 1H, J=10.2 Hz), 5.97-6.07 (m, 2H), 6.55 (dt, 1H,J=9.9, 4.0 Hz); ¹³ C-NMR (75 MHz, CDCl₃ ) δ: 27.63, 27.81, 47,87, 45.55,49.50, 52.02, 53.14, 128.43, 134.06, 139.54, 147.90, 203.76; MS m/z: 176(M⁺), 66 (100%); HRMS Calcd. C₁₂ H₁₄ O: 174.1 045 Found: 174.1063; AnalCalcd. C₁₂ H₁₄ O: C,82.72, H,8.10 Found: C,82.97, H,7.97

EXAMPLE 5

To a mixture of copper bromide-dimethyl sulfide complex (8 mg, 39 μmol)and a THF solution (4ml) of hexamethylphosphoamide (0.26 ml, 1.54 mmol), a THF solution (0.74 ml, 0.71 mmol) of 0.96M isopropenyl magnesiumbromide was added dropwise with stirring at -78° C. After ten minutes,cyclohexenone derivative (3) (R=Me, 130 mg, 0.74 mol) and a THF solution(2 ml) of trimethylsilyl chloride (0.19 ml, 1.5 mmol ) was addeddropwise to the mixture, and the mixture was stirred for one hour at thesame temperature. 5% hydrochloric acid (1 ml) was added to the resultingreaction mixture, and the mixture was stirred for 30 minutes at roomtemperature and extracted with diethyl ether. The extract was washedwith water, with a saturated aqueous solution of sodium bicarbonate andwith a saturated aqueous solution of sodium chloride. The organic layerwas dried over anhydrous magnesium sulfate, and the solvent wasdistilled away under reduced pressure. The residue was chromatographedover silica gel to obtain the colorless oily 3-substituted cyclohexanederivative (4) (R=Me, R'=isopropenyl, 138 mg, yield 86%).

α!_(D) ²⁹ +22.2° (c 1.32, CHCl₃); IR (neat): 1707, 1652 cm⁻¹ ; ¹ H-NMR(300 MHz, CDCl₃) δ:, 1.31 (s, 3H), 1.36 (dt, 1H, J=8.4, 1.8 Hz), 1.53(d, 1H, J=8.8 Hz), 1.67 (s, 3H), 1.70-1.91 (m, 2H), 2.09-2.17 (m, 2H),2.21-2.29 (m, 2H), 2.75 (br. s, 1H), 2.87 (br. s, 1H), 4.62 (s, 1H),4.72 (s, 1H), 6.10-6.15 (m, 2H); ¹³ C-NMR (75 MHz, CDCl₃) δ: 20.78,27.46, 31.86, 38.43, 44.55, 46.62, 47.41, 49.98, 52.60, 54.94, 109.75,134.76, 139.37, 147.64, 216.89; MS m/z: 216 (M⁺), 66 (100%); HRMS Calcd.C₁₅ H₂₀ O: 216.1515 Found: 216.1485; Anal Calcd. C₁₅ H₂₀ O: C,83.28,H,9.32 Found: C,83.08, H,9.37

EXAMPLE 6

A diphenyl ether solution (4 ml) of 3-substituted cyclohexanonederivative (4) (R=He, R'=isopropenyl, 118 mg, 0.54 mmol) was heated at240° C. for 30 minutes. After cooling to room temperature, the reactionmixture was chromatographed over silica gel (10 g) to obtain colorlessoily (-)-carvone (72 mg, yield 88%), α!_(D) ³⁰ -52.3° (c 1.17, CHCl₃).

We claim:
 1. A cyclohexanone derivative represented by the formula:##STR10## wherein R is alkyl, a hydrocarbon residue having at least oneunsaturated bond, aralkyl or hydrogen.
 2. A cyclohexenone derivativerepresented by the formula: ##STR11## wherein R is alkyl, a hydrocarbonresidue having at least one unsaturated bond or aralkyl.
 3. A3-substituted cyclohexanone derivative represented by the formula:##STR12## wherein R is alkyl, a hydrocarbon residue having at least oneunsaturated bond or aralkyl, R' is alkyl, a hydrocarbon residue havingat least one unsaturated bond, aralkyl, or a substituted groupcomprising hydrocarbon having trialkyl silyl in the skeleton.
 4. Amethod for producing an optically active compound represented by theformula: ##STR13## wherein R is alkyl, a hydrocarbon residue having atleast one unsaturated bond or aralkyl, or R' is alkyl, a hydrocarbonresidue having at least one unsaturated bond, aralkyl, or a substitutedgroup comprising hydrocarbon having trialkyl silyl in the skeleton, themethod comprisingusing a compound represented by formulas 1 and (1')##STR14## as a starting material, treating the compound to obtain theoptically active compound via intermediates represented, successively,by the formula (2) or (2'): ##STR15## wherein R is alkyl, a hydrocarbonresidue having at least one unsaturated bond, aralkyl or hydrogen, bythe formula (3) or (3'): ##STR16## wherein R is alkyl, a hydrocarbonresidue having at least one unsaturated bond or aralkyl, and by theformula (4) or (4'): ##STR17## wherein R is alkyl, a hydrocarbon residuehaving at least one unsaturated bond or aralkyl, R' is as indicatedabove.